US3923624A - Apparatus for the measuring and supplying a controlled quantity of a gas - Google Patents

Apparatus for the measuring and supplying a controlled quantity of a gas Download PDF

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Publication number
US3923624A
US3923624A US442472A US44247274A US3923624A US 3923624 A US3923624 A US 3923624A US 442472 A US442472 A US 442472A US 44247274 A US44247274 A US 44247274A US 3923624 A US3923624 A US 3923624A
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United States
Prior art keywords
tubular conduit
oxygen
conduit section
electrode
tubular
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Expired - Lifetime
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US442472A
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English (en)
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Nicholaas Marinus Beekmans
Leopold Heijne
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US Philips Corp
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US Philips Corp
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4075—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts

Definitions

  • ABSTRACT A Apparatus for measuring and supplying a controlled 1301 Forelg" Apphcatlon Pmmty Data quantity of oxygen, which apparatus includes a parti- Mar. 28, 1973 Netherlands 7304299 tion wall formed of a solid which has a reversible reaction with oxygen molecules and is ion-conductive, said [52] US. Cl. 204/195 S; 204/1 T partition wall carrying electrodes for measuring and [51] Int. Cl.
  • the invention relates to apparatus for measuring and supplying a controlled quantity of gaseous oxygen.
  • Such apparatus is described, for example, in British Pat. No. 1,229,610. It comprises a partition wall which is formed of a solid having a reversible reaction with oxygen molecules and being ion-conductive, said partition wall being provided on both of its surfaces with a thin metallic and/or semiconductive electrode layer, while one of the two electrode layers is electrically interrupted, one of the resulting parts being used as a measurement electrode and the other part as a controlled-supply electrode.
  • An example of such a solid is stabilized zirconium oxide which is conductive by means of oxygen ions, while the electrodes may consist of a noble metal, such as platinum.
  • the gaseous mixture the partial pressure of one of the components of which is to be measured is arranged on one side of the partition wall.
  • the reference gas On the other side of the wall there is a reference gas at a knownconstant partial pressure.
  • the reference gas selected frequently is air.
  • E const. log Pl/P2 The unknown pressure can be directly derived by measuring the E of one of the electrode pairs.
  • the other electrode pair serves to supply gas to, or to withdraw gas from, a gaseous mixture in a controlled manner. Instead of measuring a voltage between the electrodes a current is supplied from one electrode to the other in this case. Whether oxygen is supplied to the gaseous mixture or withdrawn from it depends upon the direction of the current supplied.
  • Faradays law applies to the relation between the number of coulombs involved and the quantity N of gas: N const. i.t, where i is the current and t is the duration.
  • FIG. 1 shows a known apparatus
  • FIG. 2 an embodiment of an apparatus according to the invention
  • FIG. 3 another embodiment thereof.
  • an apparatus for measuring and supplying a controlled quantity of oxygen which comprises a tube 1 made of a substance which is ion-conductive, for example stabilized zirconium oxide, a common inner electrode 2, a measuring electrode 3, a controlled supply electrode 4, an oven 5 in which the assembly is arranged, a current supply source 6, an ammeter 7 and a voltmeter 8.
  • the inner electrode 2 is split one part being disposed opposite the outer electrode 3 and the other part opposite the outer electrode 4.
  • the voltage between the measuring electrodes must depend only according to Nernsts law upon the oxygen pressures on either side of the partition wall.
  • the current passed by the part of the tube 1 lying between the controlled-supply electrodes should not measurably influence this voltage.
  • zirconium oxide is electrically conductive, in practice part of the voltage applied across the controlled-supply electrodes will always appear at the measurement electrodes.
  • This effect which may be referred to as normal crosstalk, may be kept small by making the spacing 1 between the electrode pairs large compared with the thickness s of the partition wall (see FIG. 1
  • the absolute value of the spacing need not be large: for example with a ratio l/s 5 the crosstalk factor is found to be less than 0.1 Normal crosstalk decreases about exponentially with Us.
  • zirconium oxide was found to give rise to intense polarization or blocking when the electrode forms a continuous layer impermeable to oxygen.
  • optimally reversible electrode should be highly permeable to oxygen.
  • the latter property can be achieved in the case of a substance which in itself is impermeable to oxygen, such as platinum, by using it in the form of a finely divided porous layer.
  • the particles of the layer must be in good electrical contact with one another, but at the same time a considerable part of the partition wall (zirconium oxide) must be exposed to enable oxygen to be takenup or given off.
  • high-rate transfer of electrons must be possible between the metal and the oxygen ions which move through the zirconium oxide and which just have assumed or left the gaseous state in the form of atoms or molecules.
  • Anomalous crosstalk does substantially not occur in an embodiment of the measurement and controlledsupply apparatus in which both the inner electrode and the outer electrode are split, the electric circuits connected to the split electrode pairs having no direct electric contact with one another.
  • this embodiment cannot readily be manufactured in many cases. If, for example, the partition wall has the form of a small-diameter tube it is difficult to locate the gap by which the inner electrode is split in accurate register with the outer gap. Furthermore the spacing required to reduce the normal crosstalk voltage which occurs in any case to a value below the permissible limit value may be too large, for example because the resulting travel time of the gas is too large.
  • the measuring circuit in order to fully utilize the splitting of the two electrode layers the measuring circuit must be completely separated from the controlled-supply circuit.
  • the invention enables, while eliminating the influence ofanomalous crosstalk, an apparatus to be used which has a common counter electrode for the measurement and controlled-supply circuits.
  • the said apparatus permits the use of a simple amplifier.
  • an apparatus for measuring and supplying a controlled quantity of oxygen which apparatus includes a partition wall formed of a solid which has a reversible reaction with oxygen mole- 'cules and is conductive by means of oxygen ions, said partition wall being provided on both surfaces with a thin metallic and/or semiconductive electrode layer, while one of the two electrode layers is electrically interrupted, one part being used as a measurement electrode while the other part is used as a controlled-supply electrode, is characterized in that at the location of the gap in the electrode layer the partition wall is interrupted by the interposition of a layer of a substance in which the conduction by oxygen ions is negligibly small as compared with that in the material of the partition wall.
  • a tube made of ZrO is cut into two parts which then are joined again with the interposition of such a substance.
  • the said substance may, for example, be a metal, such as platinum.
  • the electric conductivity of platinum is completely electronic; compact platinum is not permeable to oxygen in the form of a gas or of ions. Since the stabilized zirconium oxide is electrically conducting by means of oxygen ions only, an intimate contact between zirconium oxide and platinum sheet does not give rise to short-circuiting of the voltage difference set up across the zirconium oxide.
  • the two parts made of zirconium oxide may be joined by means of a melting ceramic, a glass or a glass ceramic.
  • the metal which is interposed between the two electrode halves and the conduction of which by means of oxygen ions is negligibly small as compared to that of the material of the partition wall may also be used as electric lead-through member for the inner electrode.
  • the joint between the metal and the substance which is ion-conductive is established by means of a material generally referred to as a melting ceramic (see G. H. Jonker et al. in G. H. Stewart Science of Ceramics Academic Press, London 1965).
  • a melting ceramic of the composition expressed in per cent by weight, Al O l8, SiO 40.5 and CaO41.5.
  • the joint is made by applying a suspension of the said oxide mixture to the two tube ends to be joined, drying it and subsequently heating the tube ends together with an interposed ring of platinum to a temperature of 1,375C. During this heating the oxide mixture melts and wets both platinum and ZrO so that after cooling a gas-tight joint is obtained.
  • the leakage of oxygen through the tube in this embodiment at an elevated temperature was found to be as small as the leakagethrough a tube including no platinum ring and is normal for stabilized zirconium oxide at the said temperature.
  • FIGS. 2 and 3 The two last-mentioned embodiments are shown diagrammatically in FIGS. 2 and 3.
  • reference numeral 9 denotes the interposed member which may be a platinum ring, a melting ceramic, a glass or a glass ceramic.
  • FIG. 3 shows the embodiment in which a metal in combination with a metling ceramic 10 is used as a lead-through member for the inner electrode 2.
  • Apparatus for measuring and controlling the partial pressure of oxygen comprising:
  • third tubular conduit section aligned with and spacing said first and second tubular conduit sections and forming therewith a tubular conduit cell, said third tubular conduit section being of a material which is substantially not capable of conducting electricity by the transfer or migration of oxygen ions;
  • first and second electrode layers substantially covering the outside surface respectively of said first and second tubular sections
  • a third electrode layer substantially covering the inside surface of said first, second and third tubular sections
  • first and second tubular conduit sections are made of stabilized zirconium oxide and said third tubular conduit section and said first, second and third electrode layers oxide elements with a ceramic compound.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Measuring Oxygen Concentration In Cells (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
US442472A 1973-03-28 1974-02-14 Apparatus for the measuring and supplying a controlled quantity of a gas Expired - Lifetime US3923624A (en)

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NL7304299A NL7304299A (fr) 1973-03-28 1973-03-28

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US3923624A true US3923624A (en) 1975-12-02

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US (1) US3923624A (fr)
JP (1) JPS49130291A (fr)
BE (1) BE812850A (fr)
CA (1) CA1022879A (fr)
DE (1) DE2412721A1 (fr)
FR (1) FR2223695B1 (fr)
GB (1) GB1420913A (fr)
IT (1) IT1010822B (fr)
NL (1) NL7304299A (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2339860A1 (fr) * 1976-01-30 1977-08-26 Mess & Regelungst Veb K Dispositif pour l'analyse des gaz sans prelevement
FR2364450A1 (fr) * 1976-09-10 1978-04-07 Westinghouse Electric Corp Methode et appareil de protection des electrodes detectrices d'une cellule electrochimique a electrolyte solide
US4272330A (en) * 1980-03-03 1981-06-09 Ford Motor Company Transient mode oxygen sensor and method
US4381224A (en) * 1981-04-27 1983-04-26 Ford Motor Company Step function lean burn oxygen sensor
US4384935A (en) * 1979-09-13 1983-05-24 U.S. Philips Corporation Gas analysis apparatus
US4394222A (en) * 1979-11-20 1983-07-19 Brown, Boveri & Cie Ag Method for determining the oxygen content in gases, uninfluenced by temperature variations
US4396466A (en) * 1981-04-27 1983-08-02 Ford Motor Company Absolute pressure sensor
DE3405576A1 (de) * 1983-07-20 1985-01-31 Toyota Motor Co Ltd Kraftstoff-luft-verhaeltnisfuehler und verfahren zur messung eines kraftstoff-luft-verhaeltnisses
US4741817A (en) * 1980-11-17 1988-05-03 Socapex Electrochemical sensor for the concentration of aspects in a fluid mixture and system for regulating the richness of an air-fuel mixture utilizing such a sensor
US5411644A (en) * 1993-11-03 1995-05-02 Neukermans; Armand P. Method of operated dual pump getter and oxidant sensor and regulator
US5683570A (en) * 1993-06-04 1997-11-04 Dalhousie University Gas detection method
US5879526A (en) * 1994-11-08 1999-03-09 Robert Bosch Gmbh Electrochemical measuring sensor for determining nitrogen oxides in gas mixtures
US6165336A (en) * 1995-09-29 2000-12-26 Matsushita Electric Industrial Co. Ltd. Gas sensor
US20090107893A1 (en) * 2007-10-26 2009-04-30 Becton, Dickinson And Company Deflection plate

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2942494A1 (de) * 1979-10-20 1981-04-30 Bosch Gmbh Robert Beheizbarer messfuehler fuer bestandteile von gasen, insbesondere in abgasen von brennkraftmaschinen
MX160910A (es) * 1981-03-02 1990-06-14 Babcock & Wilcox Co Aparato mejorado para detectar la presencia de constituyentes de un combustible en una mezcla de gas con exceso de oxigeno

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3216911A (en) * 1961-09-29 1965-11-09 Union Carbide Corp Method of determining gas concentration and fuel cell construction
US3514377A (en) * 1967-11-27 1970-05-26 Gen Electric Measurement of oxygen-containing gas compositions and apparatus therefor
US3525646A (en) * 1967-08-31 1970-08-25 Raffinage Cie Franc De Battery of fuel cells of solid electrolyte and the process of making these
US3654112A (en) * 1967-07-20 1972-04-04 Philips Corp Device for measuring and dosing a gas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3216911A (en) * 1961-09-29 1965-11-09 Union Carbide Corp Method of determining gas concentration and fuel cell construction
US3654112A (en) * 1967-07-20 1972-04-04 Philips Corp Device for measuring and dosing a gas
US3525646A (en) * 1967-08-31 1970-08-25 Raffinage Cie Franc De Battery of fuel cells of solid electrolyte and the process of making these
US3514377A (en) * 1967-11-27 1970-05-26 Gen Electric Measurement of oxygen-containing gas compositions and apparatus therefor

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2339860A1 (fr) * 1976-01-30 1977-08-26 Mess & Regelungst Veb K Dispositif pour l'analyse des gaz sans prelevement
FR2364450A1 (fr) * 1976-09-10 1978-04-07 Westinghouse Electric Corp Methode et appareil de protection des electrodes detectrices d'une cellule electrochimique a electrolyte solide
US4088543A (en) * 1976-09-10 1978-05-09 Westinghouse Electric Corp. Technique for protecting sensing electrodes in sulfiding environments
US4384935A (en) * 1979-09-13 1983-05-24 U.S. Philips Corporation Gas analysis apparatus
US4394222A (en) * 1979-11-20 1983-07-19 Brown, Boveri & Cie Ag Method for determining the oxygen content in gases, uninfluenced by temperature variations
US4272330A (en) * 1980-03-03 1981-06-09 Ford Motor Company Transient mode oxygen sensor and method
US4741817A (en) * 1980-11-17 1988-05-03 Socapex Electrochemical sensor for the concentration of aspects in a fluid mixture and system for regulating the richness of an air-fuel mixture utilizing such a sensor
US4381224A (en) * 1981-04-27 1983-04-26 Ford Motor Company Step function lean burn oxygen sensor
US4396466A (en) * 1981-04-27 1983-08-02 Ford Motor Company Absolute pressure sensor
DE3405576A1 (de) * 1983-07-20 1985-01-31 Toyota Motor Co Ltd Kraftstoff-luft-verhaeltnisfuehler und verfahren zur messung eines kraftstoff-luft-verhaeltnisses
US5683570A (en) * 1993-06-04 1997-11-04 Dalhousie University Gas detection method
US5411644A (en) * 1993-11-03 1995-05-02 Neukermans; Armand P. Method of operated dual pump getter and oxidant sensor and regulator
US5879526A (en) * 1994-11-08 1999-03-09 Robert Bosch Gmbh Electrochemical measuring sensor for determining nitrogen oxides in gas mixtures
US6165336A (en) * 1995-09-29 2000-12-26 Matsushita Electric Industrial Co. Ltd. Gas sensor
US20090107893A1 (en) * 2007-10-26 2009-04-30 Becton, Dickinson And Company Deflection plate
US7880108B2 (en) * 2007-10-26 2011-02-01 Becton, Dickinson And Company Deflection plate

Also Published As

Publication number Publication date
FR2223695A1 (fr) 1974-10-25
NL7304299A (fr) 1974-10-01
IT1010822B (it) 1977-01-20
GB1420913A (en) 1976-01-14
FR2223695B1 (fr) 1978-04-21
CA1022879A (fr) 1977-12-20
DE2412721A1 (de) 1974-10-10
BE812850A (fr) 1974-09-26
JPS49130291A (fr) 1974-12-13

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